WO2003082959A1 - Procede pour produire une emulsion de polyurethanne - Google Patents

Procede pour produire une emulsion de polyurethanne Download PDF

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Publication number
WO2003082959A1
WO2003082959A1 PCT/JP2003/003627 JP0303627W WO03082959A1 WO 2003082959 A1 WO2003082959 A1 WO 2003082959A1 JP 0303627 W JP0303627 W JP 0303627W WO 03082959 A1 WO03082959 A1 WO 03082959A1
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WO
WIPO (PCT)
Prior art keywords
urethane prepolymer
rotor
emulsifier
stator
emulsion
Prior art date
Application number
PCT/JP2003/003627
Other languages
English (en)
Japanese (ja)
Inventor
Tsutomu Yamada
Kazumi Mai
Masami Tsutsumi
Original Assignee
Dainippon Ink And Chemicals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dainippon Ink And Chemicals, Inc. filed Critical Dainippon Ink And Chemicals, Inc.
Priority to KR1020047007569A priority Critical patent/KR100874695B1/ko
Priority to US10/491,889 priority patent/US7253228B2/en
Priority to EP03720893A priority patent/EP1489130B1/fr
Publication of WO2003082959A1 publication Critical patent/WO2003082959A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/27—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices
    • B01F27/271—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed radially between the surfaces of the rotor and the stator
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2215/00—Auxiliary or complementary information in relation with mixing
    • B01F2215/04—Technical information in relation with mixing
    • B01F2215/0413—Numerical information
    • B01F2215/0418—Geometrical information
    • B01F2215/0427—Numerical distance values, e.g. separation, position
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2215/00—Auxiliary or complementary information in relation with mixing
    • B01F2215/04—Technical information in relation with mixing
    • B01F2215/0413—Numerical information
    • B01F2215/0436—Operational information
    • B01F2215/0481—Numerical speed values
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/27—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices
    • B01F27/271—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed radially between the surfaces of the rotor and the stator
    • B01F27/2711—Mixers with stator-rotor systems, e.g. with intermeshing teeth or cylinders or having orifices with means for moving the materials to be mixed radially between the surfaces of the rotor and the stator provided with intermeshing elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a polyurethane resin having excellent storage stability by continuously emulsifying a urethane prepolymer at least substantially not containing an organic solvent in water, and further reacting a chain extender with the urethane prepolymer.
  • the present invention relates to a method for producing Jillon. Background art
  • Polyurethane emulsions are used in various fields such as paints, inks, adhesives, textile processing, and paper processing.
  • the particles in this polyurethane emulsion have a relatively large particle size from the viewpoint of ensuring emulsion dispersion stability. Is required to be small, and it is necessary that dispersed particles of the emulsion do not easily separate and settle with time and have good storage stability.
  • a urethane prepolymer and water containing an emulsifier are premixed with a simple propeller blade type mixer or the like, and then mixed with a homogenizer or the like.
  • a method of finely dispersing under high pressure conditions has been adopted.
  • the polyurethane prepolymer is of a type containing a certain amount of an organic solvent (2 parts by weight of an organic solvent per 100 parts by weight of a urethane prepolymer solid content). 5 to 60 parts by weight).
  • a rotor having a plurality of rotor teeth on a rotating shaft provided in a cylindrical casing, and a stator having a plurality of stator teeth facing the rotor teeth are provided.
  • a method in which a mixed liquid of urethane prepolymer and water is supplied from the suction port using a milking machine having one suction port in its section, and is continuously emulsified for example, Japanese Patent Publication No. 7-6835). Publication No. 5 (pages 2 to 5) has been proposed.
  • a certain type of urethane prepolymer can be continuously emulsified to obtain an emulsion of urethane prepolymer composed of fine particles.
  • a polyurethane emulsion having excellent storage stability cannot be obtained.
  • the storage stability of the obtained emulsion is poor depending on the urethane prepolymer used, such as a type having an isocyanate and not having a hydrophilic group.
  • a type containing a hydrophilic group such as an ionic group, a type not containing such a hydrophilic group, or a type containing a very small amount thereof is appropriately selected depending on the purpose of use.
  • a production method capable of obtaining a good polyurethane emulsion even when any type of urethane prepolymer is used is used.
  • the larger the content of the hydrophilic group contained in the urethane prepolymer the smaller the particle size of the particles in the polyurethane emulsion obtained by emulsification tends to be.
  • urethane prepolymers containing no hydrophilic groups are used.
  • the content of ionic groups such as anionic groups as cationic groups and cationic groups is 0.01 equivalent or less per 100 parts by weight of the urethane prepolymer, or the content of nonionic hydrophilic 'I raw portion.
  • the dispersion particles can be reduced to some extent.
  • the viscosity of the obtained polyurethane emulsion increases, the solid concentration of the polyurethane emulsion is limited to about 30% by weight or less, and a high-concentration polyurethane emulsion is obtained. It is not possible. That is, the method has a problem in that a polyurethane emulsion which does not substantially contain an organic solvent and has excellent storage stability over time cannot be continuously obtained. Disclosure of the invention
  • An object of the present invention is to provide a method for producing a polyurethane emulsion which can substantially continuously produce a polyurethane emulsion which does not substantially contain an organic solvent and has excellent storage stability over time. It is in.
  • urethane prepolymer and water are mixed in advance and in a low-viscosity state (for example, the average particle diameter of urethane prepolymer). Since it is supplied into the emulsifier in the form of several 10 to several 100 ⁇ m (coarse dispersion state), high-speed rotating rotor teeth do not apply high shearing force uniformly, and the finely dispersed urethane prebolimer emulsion is finely dispersed. It has been found that it is difficult to obtain, and as a result, a problem that storage stability over time is poor occurs.
  • a urethane prepolymer which does not substantially contain an organic solvent and has at least two isocyanate groups in one molecule is used, and the urethane prepolymer and water are emulsified to obtain 0.1.
  • the chain stability of the urethane prepolymer is increased by continuously reacting a chain extender to improve storage stability. They found that an excellent polyurethane emulsion could be manufactured continuously, and completed the present invention.
  • the present invention provides a method for producing a polyurethane emulsion by emulsifying water in a polyurethane prepolymer, which contains substantially no organic solvent and has at least two isocyanate groups in one molecule, and extends the chain.
  • a stator portion fixedly provided in a cylindrical casing and a rotor portion fixedly provided on a rotating shaft in the casing, wherein the rotor portion has a plurality of rotor teeth.
  • the urethane pre-polymer and the water are supplied from an inlet to an emulsifier having a plurality of stator teeth in which a stator section faces rotor teeth, and having a suction port and a discharge port in the stator section. While being emulsified into the emulsion, discharged from the discharge port as an emulsion of a polyurethane prepomer having an average particle diameter of 0.1 to 2.5 ⁇ m,
  • FIG. 1 is a schematic diagram of an emulsifier used in the present invention.
  • FIG. 2 is a side sectional view of the rotor section 3 and the stator section 5 of the emulsifier used in the present invention.
  • FIG. 3 is a sectional view of the rotor section 3 of the emulsifier used in the present invention, taken along line AA.
  • the comb teeth 5a on the stator and the slit 5b between the comb teeth on the stator are omitted.
  • the casing 1 is also omitted.
  • FIG. 4 is a BB cross-sectional view of the stator section 5 of the emulsifier used in the present invention.
  • the comb teeth 3a on the rotor and the slits 3b between the comb teeth on the rotor are omitted.
  • the casing 1 is also omitted.
  • FIG. 5 is a schematic view of a liquid sending line in a production process of an emulsion of urethane prepolymer produced by the present invention.
  • FIG. 6 is a side sectional view of a rotor section 17 and a stator section 19 of a conventional emulsifier.
  • FIG. 7 is a schematic diagram of a liquid sending line of a conventional emulsifier.
  • a urethane prepolymer having substantially no organic solvent and having at least two isocyanate groups in one molecule and water are supplied to a specific emulsifier, After the urethane prepolymer is continuously emulsified in water to obtain an emulsion of the urethane prepolymer having an average particle diameter of 0.1 to 2.5 m, the urethane prepolymer is continuously reacted with a chain extender to obtain the urethane prepolymer. It is characterized in that the prepolymer is chain-extended.
  • the emulsifier used in the present invention includes, as shown in FIGS. 1 and 2, for example, a stator portion 5 having a plurality of stator teeth 6 fixedly provided in a cylindrical casing 1; A rotor having a rotor section 3 fixed to the rotating shaft 2 and having a plurality of rotor teeth 4 and having a structure in which two intake ports 8 are provided in a stator section 5 can be used.
  • a stator portion 5 having a plurality of stator teeth 6 fixedly provided in a cylindrical casing 1
  • a rotor having a rotor section 3 fixed to the rotating shaft 2 and having a plurality of rotor teeth 4 and having a structure in which two intake ports 8 are provided in a stator section 5 can be used.
  • at least two suction ports 8 are provided.
  • the plurality of rotor teeth 4 can be rotated at a high speed by the rotation of the rotating shaft 2. It is preferable that at least two suction ports 8 are provided.
  • Three or more suction ports 8 can be provided.
  • an emulsifier and other additives can flow into the urethane prepolymer and water from different inlets 8 and be uniformly mixed.
  • urethane prepolymer and water are combined as shown in Fig. 5 It is continuously supplied to the suction port 8 of the stator unit 5 by two pumps 13, which are separately provided from the reaction vessel 11 and the water tank 12.
  • the outer diameters of the rotor section 3 and the stator section 5 can be arbitrarily selected.
  • the peripheral speed X of the outermost rotor tooth among the plurality of rotor teeth 4 is preferably in the range of 30 to 70 mZs, and more preferably in the range of 40 to 60 Om / s. If the peripheral speed X of the outermost rotor tooth is within the range, a sufficiently effective shearing force for emulsification can be obtained.
  • the peripheral speed X (unit: mZ s) of the outermost rotor tooth is obtained from the value of the rotor outer diameter L (unit: m) and the number of revolutions R (unit: revolutions / minute) using the following equation [ 1].
  • the stator portion 5 is provided with at least two stator teeth 6 in a substantially ring shape
  • the rotor portion 3 is provided with at least two stator teeth 6.
  • At least two substantially ring-shaped rotor teeth 4 arranged on the side are provided.
  • a plurality of comb-shaped teeth 3a and a plurality of comb-shaped teeth 5a are provided on the rotor teeth 4 and the stator teeth 6, respectively, in a circumferential direction.
  • Slits 3b and 5b are provided between the comb teeth 3a on the rotor teeth 4 and between the comb teeth 5a on the stator teeth 6, respectively.
  • the width of the slit 3b and the slit 5b (hereinafter, referred to as the slit width) is set so that the slit width becomes narrower toward the outermost stator and rotor in order to reduce the average particle diameter of the obtained polyurethane emulsion.
  • the inner slit width is preferably 3 to 10 mm, and the outermost slit width is preferably 0.1 to 1.0 mm.
  • a gap 15 is provided between the rotor teeth 4 and the stator teeth 6, and the width of the gap 15 is preferably in the range of 100 to 100 ⁇ m, more preferably 100 ⁇ m. 5500 m. If the gap 15 between the rotor tooth 4 and the stator tooth 6 is in such a range, a fine polyurethane emulsion can be obtained.
  • the emulsifier used in the present invention has a space 7 surrounded by the rotor 3 and the stator 5 near the rotation axis.
  • the urethane prepolymer, water, and the like flowing into the casing 1 are easily moved to the outer peripheral direction by the centrifugal force generated by the rotation of the rotor section 3 near the rotation axis of the space section 7, so that the inside of the rotor section 3 It is preferable to provide the blade 9 at the bottom.
  • a urethane prepolymer and water are supplied from an inlet 8 of an emulsifier having the above-mentioned characteristics, and a high shear force is applied to the urethane prepolymer and the water. Add milk continuously.
  • a urethane prepolymer substantially free of an organic solvent and having at least two isocyanate groups in one molecule and water flow from the suction port 8 into the space 7, Due to the centrifugal force caused by the high speed rotation of the rotor portion 3 at the same time as the inflow, the rotor portion 3 flows between the rotor tooth 4 and the stator tooth 6 located at the first stage in the centrifugal direction from the center axis of rotation. It passes through a plurality of slits 3b and a plurality of slits 5b of the stator tooth 6.
  • the fluid flows between the rotor teeth 4 and the stator teeth 6 located at the second stage in the centrifugal direction from the center axis of rotation, and the shear force based on the speed gradient in the tangential direction of the rotor teeth 4 is generated by the ⁇ ⁇ Acts on the rimer and the urethane prepolymer is dispersed in the water.
  • This urethane pre-bolimer, water and force pass through a plurality of slits 3 b and a plurality of slits 5 b of the rotor teeth 4 and the stator teeth 6, and a shear force based on the velocity gradient of the rotor teeth 4 may act.
  • the process is repeated at a high speed in order, and finally, the urethane prepolymer is finely dispersed in water, and is discharged as an emulsion of a urethane prepolymer having an average particle diameter of 0.1 to 2.5 ⁇ from the discharge port.
  • a polyurethane emulsion is produced continuously by reacting a chain extender with the emulsion of the urethane prepolymer obtained in the first step to extend the chain of the urethane prepolymer. That it can.
  • a back pressure of about 1 to 3 kg / cm 2 in order to operate the emulsifier stably without generating pulsation (cavitation).
  • Inflow rate into emulsifier with urethane prepolymer and water is preferably in productivity is per hour 0. L ⁇ 4 m 3, per hour 0. 5 particularly preferably les to be 2 m 3 ,.
  • a compound having low reactivity with an isocyanate group of the urethane prepolymer or a compound having no reactive group for example, a low viscosity such as a plasticizer or an epoxy-based diluent is used.
  • a method of adding the compound of formula (1) is mentioned.
  • the ratio of the urethane prepolymer to the total weight of the urethane prepolymer and water when supplied to the emulsifier depends on the viscosity of the urethane prepolymer supplied to the emulsifier.
  • the content of the urethane prepolymer having the hydrophilic group is preferably in the range of 30 to 50% by weight.
  • the content of ⁇ urethane prepolymer having no sex groups is preferably in the range of 5 0-9 0 weight 0/0.
  • the urethane prepolymer used in the present invention does not substantially contain an organic solvent and has at least two isocyanate groups in one molecule.
  • a urethane prepolymer refers to a urethane prepolymer having an organic solvent content of 10% by weight or less. This amount of organic solvent does not require an organic solvent removal step In order to achieve this, the content is preferably 5% by weight or less, more preferably 1% by weight or less, and most preferably 0.1% by weight or less.
  • the number average molecular weight of the urethane prepolymer used in the present invention is preferably in the range of 1,000 to 20,000.
  • the urethane prepolymer used in the present invention can be produced by a conventionally known method.
  • Examples include a method of reacting a polyisocyanate compound with an active hydrogen-containing compound.
  • After a polyisocyanate compound described below is reacted with a polyol compound described below in an organic solvent the solvent is removed.
  • the former method is preferable because the solvent removal step is unnecessary.
  • the reaction is preferably carried out at a temperature in the range of 20 to 120 ° C., more preferably in the range of 30 to 100 ° C., in an equivalent ratio of the isocyanate group to the active hydrogen group, preferably 1.1: 1 to 3
  • the polyisocyanate compound is reacted with an active hydrogen-containing compound at a ratio of 1: 1, more preferably 1.2: 1 to 2: 1.
  • an excess of isocyanate group is reacted with aminosilane or the like, and the terminal group may be a reactive group other than an isocyanate group such as an alkoxysilyl group.
  • polysocyanate compound examples include 2,4-tolylene diisocyanate, 2, '6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, , 4 'diphenylmethane diisocyanate, 2, 4' diphenyl methane diisocyanate, 2, 2 'diphenyl methane diisocyanate, 3, 3'-dimethyl 1,4,4-biphenylenediiso Cyanate, 3, 3'-dimethoxy-1,4'-biphenylene diisocyanate, 3, 3'-dicrochloride 4,4'-biphenylene diisocyanate, 1,5_ naphthalene diisocyanate, 1, 5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethyl hexene
  • the active hydrogen-containing compound used in producing the urethane prepolymer used in the present invention includes a compound having a relatively high molecular weight (hereinafter, referred to as a high molecular weight compound) and a compound having a relatively low molecular weight (hereinafter, referred to as a low molecular weight compound). ) Can be used.
  • the number average molecular weight of the high molecular weight compound is preferably in the range of 300 to 100,000, more preferably in the range of 500 to 50,000.
  • the number average molecular weight of the low molecular weight compound is less than 300.
  • active hydrogen-containing compounds may be used alone or in combination of two or more.
  • high molecular weight compound among the active hydrogen-containing compounds include, for example, polyester polyols, polyether polyols, polycarbonate polyols, polyacetyl polyols, polyatarylate polyols, polyester amide polyols, and polyammonium polyols. And thiophene polyols, polybutadiene-based borolefin boryls and the like.
  • polyester polyol a polyester polyol obtained by subjecting the following glycol component and the following acid component to a dehydration condensation reaction can be used.
  • glycol component examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methynole-1.
  • Examples of the acid component that can be used in obtaining the polyester polyol include, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclohexane Pentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid Acid, bipheninoresicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and anhydride or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-bis (phenoxy) ethane-p, p
  • polyesters obtained by a ring-opening polymerization reaction of a cyclic ester compound such as -prolactone and copolymerized polyesters thereof can also be used.
  • polyether polyols include ethylene glycol, diethylene glycol cornole, triethylene glycol cornole, propylene glycol cornole, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexane.
  • One or more compounds having at least two active hydrogen atoms such as dihydroxybenzoic acid, hydroxyphthalic acid, 1,2,3-propanetrithiol, for example, ethylene oxide Propylene Nokisai de, Buchirenokisai de, styrene O key side, Epikuronorehi drill down, as tetrahydrofuran, compound I Ri is addition polymerized to a conventional method in one or more of xylene cyclohexylene and the like.
  • polycarbonate polyol examples include compounds obtained by reacting a glycolone such as 1,4-butanediol, 1,6-hexanediolone, diethylene glycolone, and the like with dipheninole carbonate and phosgene.
  • the above low molecular weight compounds are compounds containing at least two or more active hydrogens in the molecule and having a number average molecular weight of less than 300, for example, as a raw material for the above polyester polyol.
  • Glycerol trimethylolethane, trimethylolonepropane, sorbitole, pentaerythritol, and other polyhydroxy compounds; ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethinorebi Perazine, isophorone diamine, 4,4'-dihexylhexyl methanediamine, 3,3, -dimethyl-1,4,4'-dihexyl hexyl methanediamine, 1,4-dihexyl hexyldiamine , 1, 2-propanediamine, hydrazine, diethylenetriamine, triethylenetetramine, etc. And the like.
  • the average particle size of the polyurethane emulsion obtained according to the present invention depends on the presence or absence of a hydrophilic group and the content of the hydrophilic group in the polyurethane prepolymer to be used.
  • the average particle size of the polyurethane emulsion tends to be smaller than the case without the polyurethane emulsion.
  • the hydrophilic group is, specifically, an anionic group (a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc.); a cationic group (a tertiary amino group, a quaternary amino group, etc.); Alternatively, it means a nonionic hydrophilic portion (such as a group consisting of repeating units of ethylene oxide, a group consisting of repeating units of ethylene oxide and other alkylene oxide units).
  • the average particle diameter of the polyurethane emulsion is preferably small, and the storage stability is more excellent.
  • the urethane prepolymer has a hydrophilic group, it is possible to obtain an extremely finely dispersed polyurethane resin having an average particle diameter of about 0.1 to 1.0 ⁇ m, and excellent storage stability. It is suitable for applications such as paints, inks, pigment vehicles, adhesives, and plastic film primers.
  • urethane prepolymers having no ionic groups urethane prepolymers of a type having an extremely small content of ionic groups, and urethane prepolymers having a nonionic hydrophilic portion such as a polyoxyethylene chain can be used. It is preferred to use.
  • the urethane prepolymer of the type having an extremely small content of ionic groups specifically includes an ionic group such as an anionic group or a cationic group, which has a content of 0% by weight per 100 parts by weight of the urethane prepolymer. .01 Less than 1 equivalent.
  • the content of the nonionic hydrophilic portion is more than 20 parts by weight per 100 parts by weight of the urethane prepolymer, fine particles can be obtained, but the viscosity of the obtained polyurethane emulsion will increase. Therefore, the concentration of the solid content of the polyurethane emulsion is limited to about 20 to 30% by weight, which may not be preferable in some applications. Practically, the content of the nonionic biohydrophilic portion is preferably not more than 2 ° parts by weight, more preferably not more than 10 parts by weight, per 100 parts by weight of the urethane prepolymer.
  • the dispersed particles undergo sedimentation and sedimentation with the lapse of time when the average particle diameter is in the range of 0.1 to 2.5 ⁇ . It is difficult to obtain a polyurethane emulsion with excellent storage stability.
  • urethane prepolymer having an ionic group such as an anionic group or a cation group, or a hydrophilic group such as a nonionic hydrophilic portion it is also possible to use a urethane prepolymer having an ionic group such as an anionic group or a cation group, or a hydrophilic group such as a nonionic hydrophilic portion.
  • an emulsion having a small average particle diameter can be obtained.
  • a nonionic hydrophilic portion containing a repeating unit of ethylene oxide is preferable in that the finally obtained polyurethane emulsion has excellent miscibility with other types of emulsions, and When a carboxyl group and a Z or sulfonate group are introduced, it is more effective in miniaturizing particles.
  • the above-mentioned ionic group means a functional group which can become an ionic group which is hydrophilic by neutralization and contributes to self-water dispersibility.
  • the neutralizing agent used for the neutralization include a non-volatile base such as sodium hydroxide and a hydroxide hydroxide, trimethylamine, triethylamine, dimethylethanolamine, and methyl.
  • Tertiary amines such as jetanolamine and triethanolamine, and volatile bases such as ammonia can be used.
  • the ionic group is a cationic group
  • mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid and acetic acid
  • organic acids such as formic acid and acetic acid
  • the neutralization may be performed before, during, or after the polymerization of the compound having an ionic group, or during the urethanization reaction. Any after the reaction may be used.
  • a hydrophilic group into the urethane prepolymer, for example, as an active hydrogen-containing compound, a compound having at least one or more active hydrogen atoms in the molecule and having the above-mentioned hydrophilic group is used. It may be used as a raw material.
  • Compounds having at least one active hydrogen atom in the molecule and containing the above hydrophilic group include, for example, 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5 —Sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-1,4,6-disulfonic acid, 2,4-diaminotoluene-15-sulfonic acid and other sulfonic acid group-containing compounds and derivatives thereof, or derivatives thereof
  • Carboxylic acid-containing compounds such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, and 3,4-diaminobenzoic acid And their derivatives or polyester polyols obtained by copolymerizing them;
  • Tertiary amino group-containing compounds such as methyl jetanolamine, butyl jetanolamine, alkyldiisopropanolamine, and derivatives thereof, or polyester polyols or polyether polyols obtained by copolymerizing them; Group-containing compounds and their derivatives or polyester polyols or polyether polyols obtained by copolymerizing them with methyl chloride, methyl bromide, dimethyl sulfate, getyl sulfate, benzyl chloride, benzyl bromide, ethylene Reactants of quaternizing agents such as chronorehydrin, ethylene bromhydrin, epichronorehydrin, and brombutane;
  • Nonionic group-containing compounds such as polyoxypropylene copolymer daricol, polyoxyethylene-polyoxybutylene copolymer glycol, polyoxyethylene-polyoxyalkylene copolymer glycol or monoalkyl ether thereof, or a copolymer thereof.
  • Examples include polyester polyether polyols obtained by polymerization.
  • the water used in the present invention does not need to contain an emulsifier in particular when the urethane prepolymer has a hydrophilic group in the molecule, but when the urethane prepolymer does not have a hydrophilic group, it contains urethane. It is necessary to contain an emulsifier in order to finely disperse the prepolymer in water and improve the storage stability of the polyurethane emulsion.
  • emulsifiers examples include polyoxyethylene-polyoxypropylene copolymer, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrene diphenylene ether, polyoxyethylene sorbitol tetraoleate.
  • Nonionic emulsifiers such as;
  • Fatty acid salts such as sodium oleate, alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, naphthalene sulfonate sodium salts, alkyl diphenyl ether sulfonate sodium salts, etc.
  • Anionic emulsifier such as sodium oleate, alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, naphthalene sulfonate sodium salts, alkyl diphenyl ether sulfonate sodium salts, etc.
  • Nonionic anionic emulsifiers such as polyoxetylene alkyl sulfate and polyoxyethylene alkylphenyl sulfate are exemplified.
  • the amount of the emulsifier used is preferably in the range of 0.1 to 15 parts by weight, more preferably in the range of 1 to 10 parts by weight, based on 100 parts by weight of the urethane prepolymer.
  • the urethane prepolymer used in the present invention is liquid at room temperature, has high viscosity at room temperature, or has a viscosity of 200 to 100,000 at a temperature of the melting point or higher even in a solid state. High shear force when emulsifying with an emulsifier This is preferable in terms of easy workability and workability.
  • an aqueous dispersion, a stabilizer, and the like can be added to water as necessary.
  • an aqueous dispersion include emulsions such as vinyl acetate, ethylene monoacetate, acrylic, and acrylstyrene; latexes such as styrene and butadiene; acrylonitrile butadiene; and acrylic butadiene; polyethylene,
  • emulsions such as vinyl acetate, ethylene monoacetate, acrylic, and acrylstyrene
  • latexes such as styrene and butadiene
  • acrylonitrile butadiene and acrylic butadiene
  • polyethylene examples include polyolefin-based ionomers and various aqueous dispersions such as polyurethanes, polyesters, polyamides, and epoxy resins.
  • an emulsion of a urethane prepolymer having an average particle diameter of 0.1 to 2.5 ⁇ is obtained.
  • the urethane prepolymer obtained by the first step is allowed to react with a chain extender to elongate the urethane prepolymer, whereby the storage stability is excellent.
  • the polyurethane emulsion can be manufactured continuously.
  • Examples of the chain extender used in the present invention include water, ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methionolepiperazine, and 2,5-dimethyl.
  • Diamines; polyamines such as diethylenetriamine, dipropylenetriamine, and triethylenetetramine Hydrazine compounds; Sang hydrazide compounds can be mentioned. These can be used alone or in combination.
  • the step of removing the organic solvent can be omitted, and the average particle size of the emulsion particles can be reduced even if a hydrophilic group-free urethane prepolymer having a very small content is used.
  • the measurement of the average particle size and the measurement of storage stability are performed by the following methods.
  • the polyurethane emulsion was diluted to a concentration of 20% by weight, sealed in a test tube and allowed to stand, and the sedimentation state after one day had elapsed was visually observed.
  • the volume ratio of the transparent supernatant to the whole solution was visually measured to determine the storage stability. The results are shown in Table 1. The smaller the value of the “supernatant volume”, which is the volume ratio of the supernatant, the slower the sedimentation speed and the better the storage stability.
  • the peripheral speed of the rotor section 3 of the emulsifying machine was emulsified with 4 OMZ s, the Emarujo down the ⁇ urethane prepolymer having an average particle diameter of 0. 1 8 ⁇ m shown in Table 1 at a rate of per hour 5 m 3 Obtained continuously.
  • a water-diluted solution of hydrazine having an amino group equivalent to 90% of the isocyanate group was added to the mixture to extend the chain, and finally a polyurethane emulsion having a solid content of 35% by weight was obtained.
  • the emulsifier used had a rotor section 3 with a diameter of 13 Omm, a gap between the rotor teeth 4 and the stator teeth 6 of 25 ⁇ m, and a slit width of the outermost rotor teeth of 0.4 mm.
  • Example 2 >>
  • a water-diluted solution of hydrazine having an amino group equivalent to 90% of the isocyanate group was added to the solution to extend the chain, and finally a polyurethane emulsion having a solid content of 50% by weight was obtained.
  • a polyurethane emulsion having a solid content of 50% by weight was obtained.
  • Example 2 The same emulsifier as in Example 1 was used.
  • FIG. 6 An emulsifier having one inlet 22 in the stator portion 19 as shown in FIG. 6 was used.
  • reference numeral 16 is a rotation axis
  • Reference numeral 17 denotes a rotor portion
  • reference numeral 18 denotes rotor teeth
  • reference numeral 20 denotes stator teeth
  • reference numeral 21 denotes a space portion
  • reference numeral 23 denotes a discharge port.
  • the urethane prepolymer and the emulsifier were used instead of the emulsifier shown in FIG. 2 used in Example 2 and using an emulsifier having one inlet 22 in the stator part 19 as shown in FIG. without prior mixing the water, using an emulsifying machine such as converge in the mixing portion 2 9 just before the emulsifier as in FIG. 7, a urethane Prevost Rimmer per hour 0. of 2 m 3 speed, aqueous emulsifier solution per hour 0. I was allowed to flow into one of the inlet at 1 5 m 3 speed.
  • reference numeral 24 denotes a casing of an emulsifier
  • reference numeral 25 denotes a urethane pre-polymer reaction vessel
  • reference numeral 26 denotes a water tank
  • reference numeral 27 denotes a pump
  • reference numeral 28 denotes a product tank.
  • Example 1 a water-diluted solution of hydrazine having an amino group amount equivalent to 90% of the isocyanate group was added to extend the chain, and finally a polyurethane emulsion having a solid concentration of 50% by weight was obtained. .
  • the supernatant amount was 55%, and the storage stability was significantly inferior to that of Example 2.
  • the step of removing the organic solvent can be omitted, the organic solvent is not substantially contained, and the average particle diameter is 0.1 to 2.5 ⁇ m.
  • Polyethylene emulsion having excellent storage stability in a range can be continuously produced.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne une machine servant à produire une émulsion, utilisée pour produire une émulsion de polyuréthanne. Cette machine présente une partie stator (5), montée de manière fixe dans un carter cylindrique (1), et une partie rotor (3) montée de manière fixe sur un arbre de rotation (2) dans le carter (1). La partie rotor (3) présente des dents de rotor (4), tandis que la partie stator (5) comporte des dents de stator (6) opposées aux dents de rotor (4), une ouverture d'aspiration (8) et une ouverture d'évacuation (10). Le prépolymère d'uréthanne, contenant au moins deux groupes isocyanate par molécule, ainsi que de l'eau sont acheminés à travers l'ouverture d'aspiration (8). Tandis qu'ils sont émulsifiés, les matériaux sont évacués à travers l'ouverture d'évacuation (10) sous la forme d'une émulsion de prépolymère d'uréthanne présentant un diamètre moyen de particules compris entre 0,1 et 2,5 νm. L'émulsion est ensuite mise à réagir avec un allongeur de chaîne pour produire l'émulsion de polyuréthanne.
PCT/JP2003/003627 2002-03-28 2003-03-25 Procede pour produire une emulsion de polyurethanne WO2003082959A1 (fr)

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KR1020047007569A KR100874695B1 (ko) 2002-03-28 2003-03-25 폴리우레탄 에멀젼의 제조법
US10/491,889 US7253228B2 (en) 2002-03-28 2003-03-25 Method for producing polyurethane emulsion
EP03720893A EP1489130B1 (fr) 2002-03-28 2003-03-25 Procede pour produire une emulsion de polyurethanne

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BRPI0621561A2 (pt) 2006-02-22 2011-12-13 Gervais Danone Sa processo para a fabricação de um leite fermentado
ATE496686T1 (de) * 2006-12-19 2011-02-15 Dow Global Technologies Inc Vorrichtung und verfahren zur herstellung von dispersionen
ITMI20091797A1 (it) * 2009-10-19 2011-04-20 Giordano Colombo Apparecchiatura di reazione ed emulsificazione, particolarmente per emulsionare acqua e combustibile diesel e metodo di emulsificazione utilizzante tale apparecchiatura
SG188231A1 (en) 2010-08-19 2013-04-30 Meiji Co Ltd Particle size breakup device and its performance estimation method and scale up method
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US9358509B2 (en) 2010-08-19 2016-06-07 Meiji Co., Ltd. Particle size breakup apparatus having a rotor and a stator
CN103180036B (zh) 2010-08-19 2016-08-03 株式会社明治 微粒化装置的性能评价方法以及尺度上推方法
TWI604885B (zh) 2011-08-19 2017-11-11 明治股份有限公司 Microprocessing equipment
EP2868369B1 (fr) * 2013-11-01 2016-05-25 Umicore AG & Co. KG Disperseur de rotor-stator en ligne et procédé
JP6254020B2 (ja) * 2014-03-05 2017-12-27 第一工業製薬株式会社 水系ウレタンウレア樹脂組成物および製造方法、反応性乳化剤および乳化方法
CN104163293A (zh) * 2014-08-09 2014-11-26 常州市武进华瑞电子有限公司 调节型塑料颗粒存储装置
ES2719875T3 (es) 2014-11-10 2019-07-16 Eme Finance Ltd Dispositivo para mezclar agua y gasoil, aparato y proceso para producir una microemulsión de agua/gasoil
WO2016139223A1 (fr) * 2015-03-03 2016-09-09 Ineos Styrolution Group Gmbh Procédé et dispositif pour la production de composés à mouler thermoplastiques
IT201600132801A1 (it) 2016-12-30 2018-06-30 Eme International Ltd Apparato e processo per produrre liquido derivante da biomassa, biocarburante e biomateriale
WO2022265477A1 (fr) * 2021-06-18 2022-12-22 주식회사 엘지화학 Appareil de micronisation pour hydrogel de polymère superabsorbant
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US7253228B2 (en) 2007-08-07
US20040242764A1 (en) 2004-12-02
KR100874695B1 (ko) 2008-12-18
EP1489130A4 (fr) 2006-05-10
TWI286149B (en) 2007-09-01
CN1257929C (zh) 2006-05-31
KR20040093663A (ko) 2004-11-06
CN1602327A (zh) 2005-03-30
TW200304458A (en) 2003-10-01
EP1489130A1 (fr) 2004-12-22
EP1489130B1 (fr) 2011-08-10

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